Copper catalyst for fuels

ABSTRACT

This invention pertains to an improved energy-saving fuel additive for jet engines, gasoline and diesel engines, including additions to domestic heating and light industrial oils (#2 and #3) and residual or bunker fuel (#4, #5, and #6), which comprises as active ingredients a catalytic mixture of a major proportion of picric acid and a minor proportion of cupric sulfate. 
     
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     Cupric sulfate   .01-.03%                                                 
Picric acid      1-2%                                                     
Methanol         35-50%                                                   
Isopropyl alcohol                                                         
                 15-5%                                                    
Toluene          43-48%                                                   
Nitrobenzene      .6-1.0%                                                 
Primene 81R       .5-1.0%                                                 
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     Additional variations include (1) the replacement of the toluene with about 10% methanol and 90% isopropyl alcohol for toxicity reasons and (2) replacement of the toluene with 10% methanol, 45% isopropyl alcohol, and 45% kerosene as a cost-reducing factor. 
     A preferred additive is:______________________________________Cupric sulfate   .02%Picric acid      1.54%Methanol         35%Isopropyl alcohol                 15%Toluene          48.3%Nitrobenzene     .8%Primene 81R      .05%______________________________________

The present invention is an energy-saving fuel additive for gasoline anddiesel engines which more particularly includes addition to domesticheating and light industrial oil (#2 and #3) and residual and bunkerfuels (#4, #5, and #6). This fuel additive comprises as activeingredients a major proportion of picric acid and a minimum proportionof cupric sulfate (CuSO₄.no H₂ O):

    ______________________________________                                        (I)        Cupric sulfate   .01-.03%                                                     Picric acid        1-2%                                                       Methanol         35-50%                                                       Isopropyl alcohol                                                                              15-5%                                                        Toluene          43-48%                                                       Nitrobenzene     .6-1.0%                                                      Primene 81R      .5-1.0%                                           ______________________________________                                    

Additionally, cuprous sulfate may be utilized in lieu of cupric sulfate,although not preferred.

The basic additive has two variations which are included in the presentinvention. One variation replaces the toluene with a solvent ratio ofpreferred about 10% methanol and 90% isopropyl alcohol by weight.

    ______________________________________                                        (II)        Cupric sulfate   .01-.03%                                                     Picric acid        1-2%                                                       Methanol         35-50%                                                       Isopropyl alcohol                                                                              15-5%                                                        Methanol/isopropyl                                                            alcohol 10/90    43-48%                                                       Nitrobenzene     .6-1.0%                                                      Primene 81R      .5-1.0%                                          ______________________________________                                    

The methanol/isopropyl alcohol substitution may be varied up to 50/50.The purpose of the substitution for toluene lies in the lesser toxicityvalues.

A second alternative replaces toluene with about 10% methanol, 45%isopropyl alcohol, and 45% kerosene:

    ______________________________________                                        (III)       Cupric sulfate   .01-.03%                                                     Picric acid        1-2%                                                       Methanol         35-50%                                                       Isopropyl alcohol                                                                              15-5%                                                        Methanol/isopropyl                                                                             43-48%                                                       alcohol/kerosene                                                              10/45/45                                                                      Nitrobenzene     .6-1.0%                                                      Primene 81R      .5-1.0%                                          ______________________________________                                    

The methanol/isopropyl alcohol/kerosene substitution for toluene may bevaried to about 25% methanol, 25% isopropyl alcohol, and 50% kerosene.This alternative which includes kerosene is for cost conservation.

The added developments which are related to this invention but notclaimed in this application are as follows.

An additional product which is targeted towards high flash point ingasoline comprises:

    ______________________________________                                        (IV)     Green basic copper car-                                                       bonate hydroxide, Cu.sub.2 CO.sub.3 (OH).sub.2                                                      1-3%                                                    Picric acid           1-2%                                                    Methyl isobutyl ketone (MIBK)                                                                       3-7%                                                    N--butyl alcohol      10-25%                                                  Kerosene              65-74%                                                  Nitrobenzene          .04-.12%                                                Primene 81R           .02-.10%                                       ______________________________________                                    

Additionally, related to the present compositions is a diesel high flashpoint formulation comprises:

    ______________________________________                                        (V)      Elemental iron       .01-.03%                                                 Picric acid          1-2%                                                     Methyl isobutyl ketone (MIBK)                                                                      4-6%                                                     N--butyl alcohol     15-25%                                                   Kerosene             70-74%                                                   Nitrobenzene         .05-1%                                                   Primene 81R          .05-1%                                          ______________________________________                                    

PRIOR ART

Of primary interest relative to patent prior art are three patents ofDr. Harry M. Webb, assigned to XRG International, Inc. This group ofpatents; namely, U.S. Pat. Nos. 4,099,930; 4,129,421; and 4,145,190,utilizes ferrous sulfate in conjunction with picric acid and includeswater in the solvent milieu. The present additives in the majority arebased upon cupric sulfate in conjunction with picric acid in the absenceof water. Another patent is U.S. Pat. No. 1,669,181.

Of primary interest in the present application and invention is thebasic formulation which substitutes cupric sulfate for ferrous sulfatein the Webb prior art. It has been found that the present coppercomposition is more active and imparts more power to the fuel than theferrous compositions previously used. The preferred components ofadditive I are:

    ______________________________________                                        Cupric sulfate (no water)                                                                            .02%                                                   Picric acid            1.5%                                                   Methanol               35%                                                    Isopropyl alcohol      15%                                                    Toluene                48.3%                                                  Nitrobenzene           .8%                                                    Primene 81R            .5%                                                    ______________________________________                                    

The preferred components of additive II are the same as the preferredcomponents of additive I but the toluene is replaced by a combination of10% methanol and 90% isopropyl alcohol.

The preferred components of additive III are the same as the preferredcomponents of additive I but the toluene is replaced by a combination of10% methanol, 45% isopropyl alcohol, and 45% kerosene. All are percentby weight.

Related products which are included in this invention are compositionsrelated to a high flash point gasoline which utilizes the followingpreferred components:

    ______________________________________                                        Green basic copper                                                            carbonate hydroxide    2%                                                     Picric acid            1.5%                                                   Methyl isobutyl ketone 5%                                                     (MIBK)                                                                        N--butyl alcohol       20%                                                    Kerosene               71.3%                                                  Nitrobenzene           .08%                                                   Primene 81R            .05%                                                   ______________________________________                                    

Another high flash point diesel formulation utilizes the followingpreferred components:

    ______________________________________                                        Elemental iron         .1%                                                    Picric acid            1.5%                                                   Methyl isobutyl ketone 5%                                                     (MIBK)                                                                        N--butyl alcohol       20%                                                    Kerosene               73.2%                                                  Nitrobenzene           .08%                                                   Primene 81R            .05%                                                   ______________________________________                                    

THE INGREDIENTS

Copper Sulfate. The copper sulfate which is useful in this invention iscupric sulfate, preferably the dehydrated variety CuSO₄.no H₂ O.Experiments have shown that the synergistic catalytic activity of thiscompound exceeds that of iron or ferrous sulfate previously used by asubstantial degree.

Picric Acid. This trinitrophenol acts synergistically with the cuproussulfate to give the active component of this invention.

The Aromatic Solvents. Preferably as aromatic solvent, toluene isutilized. Of the alkyl benzenes possible, toluene, ortho-, meta-, andpara-xylenes are preferred and the mesitylenes are operable. In some ofthe applications herein the toluene is replaced with other less toxicsolvents.

The Alcoholic Solvents. Of the lower alkanols useful in this inventionmethyl alcohol and isopropanol are preferred, although any C₁ -C₆ loweralkanol straight- or branch-chain can be used. Of additional interest isnormal butyl alcohol which is used in the formulation designed to give ahigh flash point.

Nitrobenzene. This compound is utilized as an additional solvent. It ismiscible with alkanols and is a superior organic solvent for the picricacid.

Primene. Primenes are tertiary alkylamines which are a cross of primaryaliphatic amines of the general formula R₁ (R₂)(R₃)CNH₂ in which theamino group is linked to a tertiary carbon atom. The amines utilized inthis invention are Primene 81R and Primene JM-T, with the 81R preferred.These amines are antioxidants and stabilizers for fuel oils and jetfuels.

EXAMPLE 1

Prior to testing, all vehicles had their catalytic converters removed.The test sequence began with a baseline Federal Test Procedure (FTP) andHighway Fuel Economy test (HFET). Next replicate FTP and HFET tests wereperformed to verify data repeatability. Following this the firstadditive was combined with the commercial unleaded fuel at a ratio of 1ounce of additive for every 12 gallons of fuel. An FTP/HFET test serieswas performed and replicate tests followed immediately.

The catalytic converters were welded in position prior to the next testseries. Baseline FTP and HFET tests were conducted and replicatebaseline tests followed. The same additive used for testing withoutcatalytic converters was then added at the same 12:1 ratio. FTP/HFETtesting with additive was performed on all vehicles with replicate testsimmediately thereafter.

The catalytic converters were again removed. Next each vehicle received400 miles of mileage accumulation using the Automotive EnvironmentalSystems, Inc. highway/city mileage accumulation driving schedule. Themileage accumulation was done with XRG additive in the commercialunleaded fuel. The additive used for the mileage accumulation and thetests following mileage accumulation was not the same additive used inthe previous test series. All additives were unmarked. After mileageaccumulation the vehicles received FTP/HFET series with replicate tests.

Between the baseline FTP/HFET and the mileage accumulation with thesecond additive, the vehicles incurred an average of 1672 miles. TheChevrolet Monte Carlo (#0051) had 1591 miles; the Ford LTD (#0052) had1740 miles; and the Buick Regal (#0053) had 1686 miles. The miles wereaccumulated with and without catalytic converters, with commercialunleaded fuel and with commercial unleaded fuel with an additive.

Table 1 relates to cupric sulfate with the formulation of this inventiondesignated additive I.

Table 2 relates to ferrous sulfate using the formula as noted in WebbU.S. Pat. No. 4,145,190, column 1.

                  TABLE 1                                                         ______________________________________                                        Cupric Sulfate                                                                Fuel Economy Summary                                                                           Without    With                                              Vehicle No.                                                                            Test    Additive   Additive                                                                             % Change                                   ______________________________________                                        CX051    FTP     14.439     14.971 +3.7                                                HFET    18.933     19.760 +4.4                                       CX0052   FTP     13.724     14.669 +6.9                                                HFET    20.477     22.055 +7.7                                       CX0053   FTP     14.969     16.159 +7.9                                                HFET    19.281     21.185 +9.9                                       Fleet    FTP     14.359     15.240 +6.1                                                HFET    19.542     20.957 +7.2                                       ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Ferrous Sulfate                                                               Fuel Economy Summary                                                                           Without    With                                              Vehicle No.                                                                            Test    Additive   Additive                                                                             % Change                                   ______________________________________                                        CX0051   FTP     14.182     14.345 +1.1                                                HFET    19.125     19.380 +1.3                                       CX0052   FTP     14.088     14.999 +6.5                                                HFET    22.864     22.798 -0.3                                       CX0053   FTP     15.793     15.582 -1.3                                                HFET    20.554     19.852 -3.4                                       Fleet    FTP     14.648     14.958 +2.1                                                HFET    20.736     20.571 -0.8                                       ______________________________________                                    

I claim:
 1. A fuel additive for jet, internal combustion, and dieselengines comprising an active ingredient formulation of a mixture ofpicric acid and cupric sulfate in a relationship of about 0.01 to0.75-1.0 cupric sulfate to picric acid by weight percent in a mixedsolvent of methanol, isopropyl alcohol, toluene, nitrobenzene, and atertiary alkyl amine which is a cross of primary aliphatic amines of thegeneral formula R₁ (R₂)(R₃)CNH₂.
 2. An additive comprising the followingmake up:

    ______________________________________                                        Cupric sulfate          .01-.03%                                              Picric acid             1-2%                                                  Methanol                35-50%                                                Isopropyl alcohol       15-5%                                                 Toluene                 43-48%                                                Nitrobenzene            .6-1.0%                                               Tertiary alkyl          .5-1.0%                                               amine which is a cross of                                                     primary aliphatic amines of                                                   the general formula                                                           R.sub.1 (R.sub.2)(R.sub.3)CNH.sub.2                                           ______________________________________                                    


3. The additive according to claim 2 wherein the cupric sulfate isutilized with a solvent of about 10% methanol and 90% isopropyl alcoholin place of toluene to lessen toxicity.
 4. The additive according toclaim 2 wherein a combination solvent of 10% methanol, 45% isopropylalcohol, and 45% kerosene replaces the toluene.
 5. A method of utilizinga fuel additive for jet, internal combustion, and diesel enginescomprising an active ingredient formulation of a mixture of picric acidand cupric sulfate in a relationship of about 0.01 to 0.75-1.0 cupricsulfate to picric acid by weight percent in a mixed solvent of methanol,isopropyl alcohol, toluene, nitrobenzene, and a tertiary alkyl aminewhich is a cross of primary aliphatic amines of the general formula R₁(R₂)(R₃)CNH₂.
 6. In a method for utilizing a fuel additive for jet,internal combustion, and diesel engines which compresses the step ofutilizing an active ingredient formulation of a mixture of picric acidand cupric sulfate in a relationship of about 0.01 to 0.75-1.0 cupricsulfate to picric acid by weight percent in a mixed solvent of methanol,isopropyl alcohol, toluene, nitrobenzene, and a tertiary alkyl aminewhich is a cross of primary aliphatic amines of the general formula R₁(R₂)(R₃)CNH₂.
 7. A method for utilizing an additive for jet, internalcombustion, and diesel engines which comprises utilizing a compositionas follows:

    ______________________________________                                        Cupric sulfate          .01-.03%                                              Picric acid             1-2%                                                  Methanol                35-50%                                                Isopropyl alcohol       15-5%                                                 Toluene                 43-48%                                                Nitrobenzene            .6-1.0%                                               Tertiary alkyl          .5-1.0%                                               amine which is a cross of                                                     primary aliphatic amines of                                                   the general formula                                                           R.sub.1 (R.sub.2)(R.sub.3)CNH.sub.2                                           ______________________________________                                    


8. The method according to claim 7 wherein the cupric sulfate isutilized with a solvent of about 10% methanol and 90% isopropyl alcoholin substitution of toluene and to lessen toxicity.
 9. The methodaccording to claim 7 wherein there is utilized a combination solvent ofabout 10% methanol, 45% isopropyl alcohol, and 45% kerosene insubstitution of toluene.